In the present work, the sol-gel synthesis method was employed as strategy to obtain a magnetic and mesoporous silica-niobia material. The planned synthesis was based on the hetero-condensation of niobium and silicon alkoxide precursors, in the presence of spherical magnetite particles. The resulting material presented interesting characteristics such as magnetism, large mesopores, in the range from 20 to 50 nm, and 68 m2 g−1 of surface area. These features allowed its use as modifier of carbon paste electrode for p-nitrophenol determination, since niobia has never been used in electrochemical sensors for the determination of nitrophenol compounds. By using differential pulse voltammetry technique, the electrode can be applied in a wide range of p-nitrophenol concentration, from 10 to 490 μmol L−1, with a limit of detection of 1.2 μmol L−1 and sensitivity up to 0.60 μA L μmol−1. The proposed electrode presented good sensitivity and selectivity and it was applied in real water samples.